On Desilylation of 13‐Vertex Carborane 1,2‐Me₂Si(CH₂)₂‐1,2‐C₂B₁₁H₁₁

Abstract

The reasons for facile double desilylation of 13-vertex carborane 1,2-Me 2 Si(CH 2 ) 2 -1,2-C 2 B 11 H 11 (2) are discussed in this article. New 13-and 14-vertex ruthenacarboranes bearing the same -CH 2 SiMe 2 CH 2 -linkage have been prepared and structurally characterized for comparison. Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C 4 Si ring, Lewis acidity of Si atom and Brønsted acidity of silica surface.

Reaction of N-heterocyclic carbenes with 13-vertex closo-carboranes: synthesis and structural characterization of zwitterionic salts of 13-vertex nido-carboranes

“…The chemistry of carboranes has been dominated by 12-vertex carboranes over half a century. 1 Only in recent years has significant progress been made in the synthesis and reactivity studies of supercarboranes (carboranes with more than 12 vertices).…”

“…2 A number of 13-and 14-vertex carboranes as well as their metal complexes have been prepared and structurally characterized. [3][4][5][6][7][8][9][10][11][12][13] They share some chemical properties with 12-vertex carboranes, and on the other hand they have their own unique features. For example, 13-vertex carborane 1,2-(CH 2 ) 3 -1,2-C 2 B 11 H 11 can undergo single-electron reduction to afford a stable carborane radical anion with [2n + 3] framework electrons, 14 which accepts additional electrons to give 13vertex nido-carborane dianions.…”